CN108054368B - Silicon-based negative electrode material, preparation method thereof and application thereof in lithium ion battery - Google Patents

Silicon-based negative electrode material, preparation method thereof and application thereof in lithium ion battery Download PDF

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CN108054368B
CN108054368B CN201711321650.6A CN201711321650A CN108054368B CN 108054368 B CN108054368 B CN 108054368B CN 201711321650 A CN201711321650 A CN 201711321650A CN 108054368 B CN108054368 B CN 108054368B
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silicon
flexible polymer
negative electrode
stirring
electrode material
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CN108054368A (en
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邓志强
庞春雷
任建国
黄友元
岳敏
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BTR New Material Group Co Ltd
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BTR New Material Group Co Ltd
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Priority to CN201711321650.6A priority Critical patent/CN108054368B/en
Priority to CN202010687170.7A priority patent/CN113594455B/en
Publication of CN108054368A publication Critical patent/CN108054368A/en
Priority to EP18889184.0A priority patent/EP3726630B1/en
Priority to PL18889184.0T priority patent/PL3726630T3/en
Priority to HUE18889184A priority patent/HUE062638T2/en
Priority to US16/760,579 priority patent/US11515530B2/en
Priority to PCT/CN2018/118102 priority patent/WO2019114556A1/en
Priority to JP2019544835A priority patent/JP6928101B2/en
Priority to KR1020207018652A priority patent/KR102480641B1/en
Priority to KR1020227044110A priority patent/KR102547081B1/en
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Priority to JP2021127006A priority patent/JP7175355B2/en
Priority to US18/048,812 priority patent/US20230106786A1/en
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Abstract

The invention relates to a silicon-based negative electrode material, a preparation method thereof and application thereof in a lithium ion battery. The silicon-based negative electrode material comprises a silicon-based active substance and a composite layer which is coated on the surface of the silicon-based active substance and is composed of a flexible polymer, crystalline flake graphite and a conductive material. The method comprises the following steps: 1) dissolving a flexible polymer in a solvent; 2) adding crystalline flake graphite and a conductive material into the flexible polymer solution obtained in the step 1) under the condition of stirring; 3) adding an anti-solvent into the mixed coating liquid obtained in the step 2), and stirring; 4) adding a silicon-based active substance into the supersaturated mixed coating solution obtained in the step 3) under the condition of stirring, stirring and separating; 5) and carrying out heat treatment to obtain the silicon-based negative electrode material. The preparation method is simple, low in cost and easy to realize industrial production, and the prepared silicon-based negative electrode material has excellent electrochemical cycle and expansion inhibition performance and can prolong the service life of the lithium ion battery.

Description

Silicon-based negative electrode material, preparation method thereof and application thereof in lithium ion battery
Technical Field
The invention relates to the field of lithium ion batteries, and relates to a silicon-based negative electrode material, a preparation method and application thereof, in particular to a silicon-based negative electrode material, a preparation method and application thereof in a lithium ion battery.
Background
With the development of lithium ion batteries in large-scale application fields, performance indexes such as energy density and power density of the lithium ion batteries need to be further improved. In terms of negative electrode materials, the conventional graphitic carbon negative electrode materials have limited specific capacity (372mAh/g), and have difficulty in meeting the requirements of high-energy density batteries, and the negative electrode materials with high specific capacity become the current research focus. Silicon-based materials are of interest because they have a theoretical specific capacity of up to 4200 mAh/g. But due to the serious volume effect and poor conductivity, the silicon negative electrode material has low reversible capacity and poor cycle stability. In order to solve the above-mentioned problems of the silicon-based materials, researchers have conducted a great deal of experimental studies, such as conductive polymer coating, carbon coating, compounding with metal oxides, nanocrystallization, porosification, and the like.
For example, patent CN 106229495 a discloses a silicon-based negative electrode material coated with a conductive polymer and a preparation method thereof. The technical key points are that a silicon-based material is coated with a conductive polymer (polythiophene, polyaniline and polypyrrole) through in-situ polymerization, sodium alginate is added to enhance stability, and expansion of the three-dimensional network structure buffer silicon material is constructed. CN 105186003 a discloses a method for preparing a high capacity lithium ion battery negative electrode material, which comprises dispersing a polymer, a conductive agent and a non-carbon negative electrode material into a suitable solvent to form a uniform emulsion, then freezing or spray drying to obtain a uniform black powder material, drying under vacuum to obtain a conductive polymer coated high capacity negative electrode material, and improving the volume change of the non-carbon negative electrode during the circulation process by using the polymer.
Therefore, the development of a silicon negative electrode material with excellent cycle performance and low volume expansion effect and a preparation method thereof are still technical problems in the field.
Disclosure of Invention
In view of the above problems in the prior art, an object of the present invention is to provide a silicon-based negative electrode material, a preparation method thereof, and a use thereof in a lithium ion battery, wherein the silicon-based negative electrode material has excellent electrochemical cycling and expansion inhibition properties, and can prolong the service life of the lithium ion battery. The preparation method has the advantages of simple and effective process, low cost, easy realization of industrialization and green and environment-friendly production process.
In order to realize the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a silicon-based negative electrode material, which comprises a silicon-based active material and a composite layer coated on the surface of the silicon-based active material and composed of a flexible polymer and a conductive material, wherein the conductive material comprises crystalline flake graphite and a nanocarbon material.
In the silicon-based negative electrode material, the crystalline flake graphite is completely attached to the surface of the silicon-based active material, the high-strength flexible polymer is coated on the surfaces of the silicon-based active material and the crystalline flake graphite, the nano-carbon material fills the area, which is not attached and coated, of the surface of the silicon-based active material, the three materials are combined together to form a composite layer, the three materials can effectively inhibit the expansion of the silicon-based material under the cooperation effect, and the coated silicon-based negative electrode material is high in conductivity and stable in conductivity, so that the silicon-based negative electrode material provided by the invention is very suitable for a lithium ion battery and has excellent cyclic expansion performance.
The following is a preferred technical solution of the present invention, but not a limitation to the technical solution provided by the present invention, and the technical objects and advantageous effects of the present invention can be better achieved and achieved by the following preferred technical solution.
The particle size of the silicon-based active substance is 0.5-100 μm, such as 0.5 μm, 2 μm, 5 μm, 10 μm, 20 μm, 35 μm, 50 μm, 70 μm, 80 μm, 90 μm, or 100 μm, and the like.
Preferably, the thickness of the composite layer is in the range of 10-100nm, such as 10nm, 20nm, 30nm, 45nm, 60nm, 70nm, 80nm, 85nm, 90nm, 95nm, or 100nm, and the like.
Preferably, the silicon-based active material comprises Si, SiOxOr a silicon alloy, wherein 0<x is less than or equal to 2. But are not limited to the silicon-based actives listed above, other silicon-based actives commonly used in the artSubstances such as carbon coated silicon oxides may also be used in the present invention.
Preferably, the flexible polymer is a natural flexible polymer and/or a synthetic flexible polymer.
The "natural flexible polymer and/or synthetic flexible polymer" according to the present invention means: can be a natural flexible polymer, a synthetic flexible polymer, or a mixture of a natural flexible polymer and a synthetic flexible polymer.
Preferably, the flexible polymer is any one or a combination of at least two of polyolefin and its derivatives, polyvinyl alcohol and its derivatives, polyacrylic acid and its derivatives, polyamide and its derivatives, carboxymethyl cellulose and its derivatives, or alginic acid and its derivatives, as typical but non-limiting examples: combinations of polyolefins and polyvinyl alcohols, combinations of polyvinyl alcohols and carboxymethylcellulose, combinations of carboxymethylcellulose and alginic acid, combinations of polyamides and derivatives of carboxymethylcellulose, combinations of polyolefins, derivatives of polyolefins and polyacrylic acids, combinations of polyvinyl alcohols, derivatives of polyamides and alginic acid, combinations of polyolefins, polyvinyl alcohols, derivatives of polyacrylic acids, polyamides and alginic acid, and the like.
Preferably, the flexible polymer is a polyolefin and derivatives thereof, a combination of a polyolefin and derivatives thereof and alginic acid and derivatives thereof.
Preferably, the flexible polymer has a weight average molecular weight of 2000-.
As a preferred embodiment of the negative electrode material of the present invention, the flexible polymer contains a thermal crosslinking functional group (also referred to as a thermally crosslinkable functional group) including any one or a combination of at least two of an epoxy group, a carboxyl group, a hydroxyl group, an amino group, a double bond, and a triple bond.
Preferably, the flake graphene is natural flake graphite and/or artificial flake graphite.
Preferably, the conductive material is a combination of flake graphite and a nanocarbon material. When the conductive material is just a mixture of the two materials, the two materials can be better matched with the silicon-based composite material to play a role in inhibiting the expansion of the silicon-based material, and the conductivity and the conductive stability are further improved.
The natural flake graphite and/or artificial flake graphite of the invention refers to: the graphite can be natural crystalline flake graphite, artificial crystalline flake graphite or a mixture of natural crystalline flake graphite and artificial crystalline flake graphite.
Preferably, the nanocarbon-based material comprises any one of or a combination of at least two of conductive graphite, graphene, carbon nanotubes or carbon nanofibers.
Preferably, the mass percentage of the flexible polymer is 0-10% and does not contain 0, such as 0.5%, 1%, 1.5%, 2%, 3%, 4%, 5%, 6.5%, 8%, 9%, 10%, etc., preferably 3-7%, based on 100% of the total mass of the silicon-based active material.
Preferably, the mass percentage of the crystalline flake graphite is 0 to 20% and does not include 0, for example, 0.5%, 1%, 3%, 3.5%, 5%, 6%, 8%, 10%, 12%, 13%, 15%, 16%, 18%, 20%, or the like, preferably 5 to 10%, based on 100% of the total mass of the silicon-based active material.
Preferably, the nanocarbon type material is 0 to 5% by mass, excluding 0, for example, 0.5%, 1%, 2%, 2.5%, 3%, 4%, 5%, or the like, preferably 1 to 3% by mass, based on 100% by mass of the total silicon-based active material.
In a second aspect, the present invention provides a method for preparing a silicon-based anode material according to the first aspect, the method comprising the steps of:
(1) dissolving a flexible polymer in a solvent to obtain a flexible polymer solution;
(2) adding a conductive material containing crystalline flake graphite and a nano-carbon material into the flexible polymer solution under the condition of stirring to obtain a mixed coating solution;
(3) adding an anti-solvent into the mixed coating liquid, and stirring to obtain supersaturated mixed coating liquid;
(4) under the condition of stirring, adding a silicon-based active substance into the supersaturated mixed coating solution, stirring and separating to obtain a precursor of the negative electrode material;
(5) and carrying out heat treatment on the anode material precursor to obtain the silicon-based anode material.
The method of the invention disperses the silicon-based active material into the supersaturated solution of the flexible polymer dispersed with the crystalline flake graphite and the nano-carbon material, utilizes the characteristics of the supersaturated solution to gradually coat the polymer on the surface of the silicon-based active material, and simultaneously leads the crystalline flake graphite and the conductive material dispersed in the solution to be adhered to the surface of the silicon-based active material through the traction and binding action of the polymer.
In the silicon-based negative electrode material prepared by the method, the very good adhesiveness of the crystalline flake graphite and the function of filling the gap by the nano carbon material are utilized, so that the coated material has a stable structure, high conductivity and stable conductivity.
As a preferable technical scheme of the method of the invention, the flexible polymer in the step (1) contains a thermal crosslinking functional group, and the thermal crosslinking functional group comprises any one or a combination of at least two of epoxy, carboxyl, hydroxyl, amino, double bonds or triple bonds. In the preferred technical scheme, the flexible polymer contains a large number of crosslinkable functional groups, and crosslinking is carried out in subsequent heat treatment, so that the strength of the coating layer is enhanced to inhibit the expansion of the material in the circulating process.
Preferably, the solvent in step (1) is any one or a combination of at least two of water, methanol, ethanol, polyvinylpyrrolidone, isopropanol, acetone, petroleum ether, tetrahydrofuran, ethyl acetate, N-dimethylacetamide, N-dimethylformamide, N-hexane or halogenated hydrocarbon.
Preferably, after the flexible polymer is dissolved in the solvent in the step (1), stirring is performed at a temperature of 25 to 100 ℃ such as 25 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃ or 100 ℃.
Preferably, the conductive material containing flake graphite and nanocarbon materials in the step (2) is: flake graphite and nanocarbon materials. When the conductive material is just a mixture of the two materials, the two materials can be better matched with the silicon-based composite material to play a role in inhibiting the expansion of the silicon-based material, and the conductivity and the conductive stability are further improved.
Preferably, after the conductive material containing the flake graphite and the nanocarbon-based material is added to the flexible polymer solution in the step (2), stirring is continued for 2-4h, such as 2h, 2.5h, 3h, 3.5h or 4 h.
Preferably, the antisolvent in the step (3) is a poor solvent for the flexible polymer, and is selected from any one or a combination of at least two of methanol, ethanol, polyvinylpyrrolidone, isopropanol, acetone, petroleum ether, tetrahydrofuran, ethyl acetate, N-dimethylacetamide, N-dimethylformamide, N-hexane, and a halogenated hydrocarbon.
Preferably, the stirring time in step (3) is 1-2h, such as 1h, 1.2h, 1.5h, 1.6h, 1.8h or 2h, etc.
Preferably, the silicon-based active substance is added into the supersaturated mixed coating solution in the step (4), and then the mixture is stirred for 2 to 4 hours at a temperature of between 25 and 80 ℃. The stirring temperature is, for example, 25 ℃, 30 ℃, 40 ℃, 45 ℃, 50 ℃, 60 ℃, 70 ℃ or 80 ℃; the stirring time is, for example, 2h, 2.5h, 3h, 3.2h, 3.5h or 4h, etc.
Preferably, the separation mode in step (4) includes any one of atmospheric filtration, vacuum filtration or centrifugation, but is not limited to the above-mentioned separation modes, and other separation modes commonly used in the art to achieve the same effect can also be used in the present invention.
Preferably, the temperature of the heat treatment in step (5) is 100-.
Preferably, the time of the heat treatment in the step (5) is 2-12h, such as 2h, 4h, 5h, 6.5h, 8h, 10h, 11h or 12h, etc.
In the method, the precursor of the cathode material obtained in the step (4) is a silicon-based material coated by crystalline flake graphite, a nano carbon material and a flexible polymer, and after the heat treatment in the step (5), the flexible polymer is crosslinked through a crosslinkable group, so that the strength of the coating layer is enhanced to inhibit the expansion of the material in the circulation process.
As a further preferred technical solution of the method of the present invention, the method comprises the steps of:
(1) dissolving a flexible polymer containing a thermal crosslinking functional group in a solvent, and stirring at 25-100 ℃ to obtain a flexible polymer solution;
(2) adding crystalline flake graphite and a nano-carbon material into the flexible polymer solution under the condition of stirring, and continuously stirring for 2-4h after the addition is finished to obtain a mixed coating solution;
(3) adding an anti-solvent into the mixed coating liquid, and stirring for 1-2h to obtain supersaturated mixed coating liquid;
(4) under the condition of stirring, adding a silicon-based active substance into the supersaturated mixed coating solution, stirring for 2-4h at 25-80 ℃, and separating to obtain a cathode material precursor;
(5) carrying out heat treatment on the anode material precursor at the temperature of 150-250 ℃ for 2-12h to obtain a silicon-based anode material;
wherein the anti-solvent is a poor solvent for the flexible polymer containing the thermal crosslinking type functional group.
In a third aspect, the present invention provides an anode comprising the silicon-based anode material of the first aspect.
In a fourth aspect, the present invention provides a lithium ion battery comprising the negative electrode of the third aspect.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention utilizes the characteristic of polymer supersaturated solution, when polymer precipitates are coated on a silicon-based active material, the crystalline flake graphite is firmly attached to the surface of the silicon-based active material and the nano carbon material is firmly filled in gaps through the traction and binding action of the polymer, the electric connection is maintained in the cyclic expansion process of the silicon-based active material, the combined action of the crystalline flake graphite completely attached to the surface of the silicon-based active material, the high-strength polymer coating coated on the surface of the silicon-based active material and the nano carbon material filled in the gaps can effectively inhibit the expansion of the silicon-based active material, and meanwhile, the prepared coated silicon-based negative electrode material has excellent performance due to the attachment of the crystalline flake graphite and the gap filling of the nano carbon material, is very suitable for a lithium ion battery, has high conductivity and stable conductivity, and is suitable for lithium ion batteries, The combined action of the flexible polymer coating and the nano carbon material filling obviously improves the cycle expansion inhibition performance of the silicon-based active material and prolongs the service life of the lithium ion battery.
(2) The preparation method has the advantages of cheap raw materials, simple and effective process, mild conditions, low requirements on equipment, low cost and easy large-scale production. Meanwhile, no toxic and harmful intermediate product is generated in the preparation process, and the production process is green and environment-friendly.
Drawings
Fig. 1 is a graph showing the 50-cycle capacity retention rate of a battery using the silicon-based negative electrode material for lithium ion batteries obtained in example 3 of the present invention.
Detailed Description
In order to more clearly explain the objects, technical solutions and technical effects of the present invention, the present invention will be described in detail below with reference to specific embodiments and accompanying drawings.
Example 1
The embodiment provides a silicon-based negative electrode material for a lithium ion battery, which is prepared by the following method:
dissolving 4g of polyacrylic acid in 100g of distilled water, fully dissolving at 40 ℃, adding 1g of carbon nanofiber and 5g of crystalline flake graphite CSG-3 under the condition of stirring, adding 200g of ethanol after stirring for 2 hours, continuously stirring for 0.5 hour, adding 90g of SiOx(x ═ 1.0) was added thereto under stirring, stirred at 60 ℃ for 2 hours, cooled to room temperature, the material was separated by suction filtration, and thenHeat treating in a drying oven at 180 deg.C for 4 hr, cooling, and taking out to obtain corresponding polyacrylic acid, CSG-3 and SiO coated with carbon nanofiberxThe cathode material is a silicon-based cathode material for a lithium ion battery.
Example 2
The embodiment provides a silicon-based negative electrode material for a lithium ion battery, which is prepared by the following method:
dissolving 2.5g polyacrylic acid in 100g distilled water, dissolving at 40 deg.C, adding 0.5g carbon nanotube and 3g scale graphite CSG-3 under stirring, stirring for 4 hr, adding 200g ethanol, stirring for 0.5 hr, adding 95g SiOxadding/C (x is 1.0) under stirring, stirring at 60 deg.C for 2 hr, cooling to room temperature, vacuum filtering to separate out material, heat treating in 180 deg.C drying oven for 4 hr, cooling, and taking out corresponding polyacrylic acid, CSG-3 and carbon nanotube coated SiOxthe/C cathode material is a silicon-based cathode material for the lithium ion battery.
Example 3
The embodiment provides a silicon-based negative electrode material for a lithium ion battery, which is prepared by the following method:
dissolving 2g of polyacrylic acid and 1g of sodium carboxymethylcellulose in 100g of distilled water, fully dissolving at 50 ℃, adding 1g of graphene and 3g of flake graphite CSG-3, stirring for 4 hours, adding 200g of methanol, continuously stirring for 1 hour, and adding 90g of SiOxAnd C (x is 1.0), stirring for 4 hours at the temperature of 50 ℃, cooling to room temperature, centrifugally separating the material, then placing the material in a drying box at the temperature of 250 ℃ for heat treatment for 4 hours, cooling, and taking out the material to obtain the corresponding SiOx/C negative electrode material coated by polyacrylic acid-sodium carboxymethyl cellulose, CSG-3 and graphene, namely the silicon-based negative electrode material for the lithium ion battery.
Fig. 1 is a graph of 50-cycle capacity retention rate of a battery made of the silicon-based negative electrode material for the lithium ion battery obtained in the embodiment, and it can be seen from the graph that the 50-cycle capacity retention rate of the battery reaches 91.2%.
Example 4
The embodiment provides a silicon-based negative electrode material for a lithium ion battery, which is prepared by the following method:
dissolving 3g of polyvinyl alcohol in 100g of distilled water, fully dissolving at the temperature of 90 ℃, adding 1g of carbon nano tube and 5g of flake graphite CSG-3 under the condition of stirring, adding 100g of acetone after stirring for 2.5 hours, continuously stirring for 2 hours, adding 100g of SiOxadding/C (x is 1.0) into the mixture under stirring, stirring the mixture for 2.5 hours at the temperature of 80 ℃, cooling the mixture to room temperature, filtering the mixture to separate out a material, then placing the material in a drying box at the temperature of 200 ℃ for heat treatment for 6 hours, and taking the material out after cooling to obtain the corresponding silicon-based negative electrode material for the lithium ion battery.
Example 5
Dissolving 5g of alginic acid in 150g of distilled water, fully dissolving at 60 ℃, adding 2g of conductive graphite and 2g of flake graphite CSG-3 under the condition of stirring, adding 200g of ethanol after stirring for 3 hours, continuously stirring for 1.5 hours, and adding 100g of SiOxAnd (x is 1.0), adding the mixture under stirring, cooling to room temperature after stirring for 4 hours at the temperature of 35 ℃, filtering to separate out the material, then placing the material in a drying box at the temperature of 100 ℃ for heat treatment for 12 hours, cooling and taking out to obtain the corresponding silicon-based negative electrode material for the lithium ion battery.
Example 6
Dissolving 4g of polyamide in a mixed solution of 80g of ethanol and 20g of isopropanol, fully dissolving at 50 ℃, adding 0.5g of carbon nanofiber and 3g of flake graphite CSG-3 under the condition of stirring, adding 150g of petroleum ether after stirring for 3.5 hours, continuing stirring for 1.5 hours, and adding 100g of SiOxadding/C (x is 1.0) into the mixture under stirring, cooling to room temperature after stirring for 2 hours at the temperature of 80 ℃, filtering to separate out the material, then placing the material in a drying box at 375 ℃ for heat treatment for 2 hours, cooling and taking out to obtain the corresponding silicon-based negative electrode material for the lithium ion battery.
Comparative example 1
Comparative example 1 is SiOxa/C negative electrode material, wherein x is 1.0.
The anode materials prepared in the embodiments 1-6 are applied to lithium ion batteries, and the numbers are respectively SI-1, SI-2 and SI-3. SI-4, SI-5 and SI-6. As a reference group, the SiO of comparative example 1 was usedxand/C (x is 1.0) is used as a negative electrode material to prepare a lithium ion battery with the number of Ref.
SiO of the anode materials and reference group prepared in examples 1 to 6 abovexMixing the/C (x is 1.0) with sodium carboxymethylcellulose, styrene butadiene rubber, conductive graphite (KS-6) and carbon black (SP) according to a ratio of 92:2:2:2:2 to prepare slurry, uniformly coating the slurry and drying the slurry on copper foil to prepare a negative pole piece, assembling the negative pole piece into a button cell in an argon atmosphere glove box, wherein a diaphragm is a polypropylene microporous membrane, an electrolyte is 1mol/L lithium hexafluorophosphate (a solvent is a mixed solution of ethylene carbonate, methyl ethyl carbonate and dimethyl carbonate), and a counter electrode is a metal lithium piece.
The 4 groups of batteries are tested for 50 weeks in a circulating way, the voltage interval is 0.005V-1.5V, and the current density is 50 mA/g. And calculating the capacity retention rate after the cycle test, disassembling the lithium ion battery, and measuring the thickness of the negative pole piece.
Wherein the 50-cycle capacity retention rate is 50-cycle discharge capacity/first-cycle discharge capacity 100%, and the results are shown in table 1; the negative electrode sheet thickness 50 cycles expansion ratio (thickness after 50 cycles-thickness of uncharged sheet)/thickness of uncharged sheet 100%, results are shown in table 1.
Table 1: 50-cycle capacity retention rate and pole piece expansion rate of each battery
Figure BDA0001504886740000111
Figure BDA0001504886740000121
The test results in table 1 show that, in the battery using the silicon-based material for lithium ion battery of the present invention as the negative active material, the 50-cycle capacity retention rate and the pole piece expansion rate are both significantly improved, which indicates that the silicon-based material for lithium ion battery of the present invention can effectively inhibit the expansion of the pole piece and the peeling of the active material during the electrochemical cycle process, thereby significantly improving the cycle performance of the lithium ion battery.
The applicants state that the examples described in this specification are intended to illustrate the invention, and that the particular materials, formulation proportions and reaction conditions referred to above are nothing more than the particular embodiments of the invention in which they are described above, and are not intended to limit the invention, i.e. they do not imply that the invention must be practiced in the manner described in detail. It should be understood by those skilled in the art that the technology realized by the above-mentioned contents of the present invention is within the scope of the present invention, and any modifications to the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope of protection and disclosure of the present invention.

Claims (31)

1. The silicon-based negative electrode material is characterized by comprising a silicon-based active material and a composite layer which is coated on the surface of the silicon-based active material and is composed of a flexible polymer and a conductive material;
wherein the conductive material contains crystalline flake graphite and a nano-carbon material;
the mass percent of the flexible polymer is 0-10% and does not contain 0, based on the total mass of the silicon-based active material as 100%;
the mass percent of the crystalline flake graphite is 0-20% and does not contain 0, wherein the total mass of the silicon-based active material is 100%;
the flexible polymer contains a thermal crosslinking functional group, and the crosslinking functional group comprises any one or a combination of at least two of epoxy, carboxyl, hydroxyl, amino, double bonds or triple bonds.
2. The negative electrode material of claim 1, wherein the silicon-based active material has a particle size of 0.5 to 100 μm.
3. The anode material according to claim 1, wherein the composite layer has a thickness of 10 to 100 nm.
4. The anode material of claim 1, wherein the silicon-based active material comprises Si, SiOxOr a silicon alloy, wherein 0<x≤2。
5. The negative electrode material of claim 1, wherein the flexible polymer is a natural flexible polymer and/or a synthetic flexible polymer.
6. The negative electrode material of claim 1, wherein the flexible polymer is any one or a combination of at least two of polyolefin and its derivatives, polyvinyl alcohol and its derivatives, polyacrylic acid and its derivatives, polyamide and its derivatives, carboxymethyl cellulose and its derivatives, or alginic acid and its derivatives.
7. The negative electrode material of claim 6, wherein the flexible polymer is a polyolefin and derivatives thereof, a combination of a polyolefin and derivatives thereof and alginic acid and derivatives thereof.
8. The negative electrode material as claimed in claim 1, wherein the flexible polymer has a weight average molecular weight of 2000-1000000.
9. The negative electrode material as claimed in claim 7, wherein the flexible polymer has a weight average molecular weight of 100000-500000.
10. The negative electrode material of claim 1, wherein the flake graphite is natural flake graphite and/or artificial flake graphite.
11. The negative electrode material of claim 1, wherein the conductive material is a combination of flake graphite and a nanocarbon-based material.
12. The anode material of claim 1, wherein the nanocarbon-based material comprises any one or a combination of at least two of conductive graphite, graphene, carbon nanotubes, or carbon nanofibers.
13. The negative electrode material of claim 1, wherein the mass percentage of the flexible polymer is 3 to 7% based on 100% by mass of the total mass of the silicon-based active material.
14. The negative electrode material as claimed in claim 1, wherein the crystalline flake graphite is 5 to 10% by mass based on 100% by mass of the silicon-based active material.
15. The negative electrode material according to claim 1, wherein the nanocarbon-based material is 0 to 5% by mass and does not contain 0, based on 100% by mass of the total silicon-based active material.
16. The negative electrode material of claim 15, wherein the nanocarbon-based material is 1 to 3% by mass based on 100% by mass of the total silicon-based active material.
17. A method for preparing a silicon-based anode material according to any one of claims 1 to 16, characterized in that the method comprises the following steps:
(1) dissolving a flexible polymer in a solvent to obtain a flexible polymer solution;
(2) adding a conductive material containing crystalline flake graphite and a nano-carbon material into the flexible polymer solution under the condition of stirring to obtain a mixed coating solution;
(3) adding an anti-solvent into the mixed coating liquid, and stirring to obtain supersaturated mixed coating liquid;
(4) under the condition of stirring, adding a silicon-based active substance into the supersaturated mixed coating solution, stirring and separating to obtain a precursor of the negative electrode material;
(5) carrying out heat treatment on the anode material precursor to obtain a silicon-based anode material;
the flexible polymer in the step (1) contains a thermal crosslinking functional group, wherein the thermal crosslinking functional group comprises any one or a combination of at least two of epoxy, carboxyl, hydroxyl, amino, double bonds or triple bonds.
18. The method according to claim 17, wherein the solvent in step (1) is any one or a combination of at least two of water, methanol, ethanol, polyvinylpyrrolidone, isopropanol, acetone, petroleum ether, tetrahydrofuran, ethyl acetate, N-dimethylacetamide, N-dimethylformamide, N-hexane, or a halogenated hydrocarbon.
19. The method of claim 17, wherein the step (1) comprises stirring the flexible polymer at 25-100 ℃ after dissolving the flexible polymer in the solvent.
20. The method according to claim 17, wherein the conductive material comprising flake graphite and nanocarbon-based material of step (2) is: flake graphite and nanocarbon materials.
21. The method according to claim 17, wherein the stirring of step (2) is continued for 2-4 hours after adding the conductive material comprising the flake graphite and the nanocarbon material to the flexible polymer solution.
22. The method according to claim 17, wherein the antisolvent in the step (3) is a poor solvent for the flexible polymer, and is selected from any one of or a combination of at least two of methanol, ethanol, polypyrrolidone, isopropanol, acetone, petroleum ether, tetrahydrofuran, ethyl acetate, N-dimethylacetamide, N-dimethylformamide, N-hexane, and a halogenated hydrocarbon.
23. The method of claim 17, wherein the stirring of step (3) is carried out for a period of 1-2 hours.
24. The method of claim 17, wherein the silicon-based active material is added to the supersaturated mixed coating solution in step (4), and the mixture is stirred at 25 to 80 ℃ for 2 to 4 hours.
25. The method of claim 17, wherein the separating in step (4) comprises any one of atmospheric filtration, vacuum filtration or centrifugation.
26. The method as claimed in claim 17, wherein the temperature of the heat treatment in the step (5) is 100-400 ℃.
27. The method as claimed in claim 26, wherein the temperature of the heat treatment in the step (5) is 150 ℃ to 250 ℃.
28. The method of claim 17, wherein the heat treatment of step (5) is performed for a period of 2-12 hours.
29. The method according to claim 17, characterized in that it comprises the steps of:
(1) dissolving a flexible polymer containing a thermal crosslinking functional group in a solvent, and stirring at 25-100 ℃ to obtain a flexible polymer solution;
(2) adding crystalline flake graphite and a nano-carbon material into the flexible polymer solution under the condition of stirring, and continuously stirring for 2-4h after the addition is finished to obtain a mixed coating solution;
(3) adding an anti-solvent into the mixed coating liquid, and stirring for 1-2h to obtain supersaturated mixed coating liquid;
(4) under the condition of stirring, adding a silicon-based active substance into the supersaturated mixed coating solution, stirring for 2-4h at 25-80 ℃, and separating to obtain a cathode material precursor;
(5) carrying out heat treatment on the anode material precursor at the temperature of 150-250 ℃ for 2-12h to obtain a silicon-based anode material;
wherein the anti-solvent is a poor solvent for the flexible polymer containing the thermal crosslinking type functional group.
30. A negative electrode comprising the silicon-based negative electrode material according to any one of claims 1 to 16.
31. A lithium ion battery comprising the negative electrode of claim 30.
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